Viscosity reduction of petroleum



Patented Nov. 30, 1948 VISCOSITY REDUCTION OF PETROLEUM MAHOGANY SULFONATE HYDROCAR- BON SOLUTIONS Jacob Faust, Belleville,, N. J assignor to L. Sonneborn Sons, Inc., a corporation of Delaware No Drawing.

1 This invention relates to new and useful improvements in the viscosity reduction of petroleum mahogany sulfonate hydrocarbon solutions.

Petroleum mahogany sulfonate solutions in organic solvents of the water immiscible type are used for a variety of purposes such as wetting agents, emulsifying agents and thelike. Qrdinary petroleum mahogany sulfon'ates impart to their solutions a relatively high viscosity. In some cases this high viscosity is not critical regarding the purpose for which the sulfonate solutions are to be used. There are, however, many cases in which a relatively high viscosity is undesirable or-detrimentalto their intended use or application. This is, for example, true in textile processing such as of wool, worsted, rayon, viscose or the like in which the various processing steps involved inthe conversionof the raw materials into fibres, the formation of the fibres into threads and the weaving of the threads into fabric, require the presence of a lubricating agent having a Saybolt viscosity of below 600 and preferably below 300 seconds Saybolt at 100 F. The latter is particularly true of textile lubricants used in the processing of synthetic fibres. In the case of textile processing it is for instance desirable to have a hydrocarbon textile lubricant composition with a sulfonate content of in excess of 28% mahogany sulfonates so as to render the composition not only readily and spontaneously emulsiflable but also to make the same readily wettable or rewettable on the fibre to thereby impart to the textile material substantial self scourability. Hydrocarbon solutions of the textile lubricant type and containing in excess of 28% of petroleum mahogany sulfonates possess, however, a viscosity far in excessof 600 seconds Saybolt at 100 F.

and usually a viscosity in excess of 1000 seconds" Saybolt at 100 F. For this reason it has been necessary in the past in such cases to limit the sul'fonate content to a maximum of approximately 15% in order not to exceed the usable viscosity for textile material treating purposes.

Another example is the use of petroleum mahogany sulfonates in the compounding of cutting oil bases in which the relatively high viscosity and tackiness imparted to the composition by the sulfonates is an undesirable aspect interfering in many respects with the proper ease of application and use.

The relatively high viscosity of petroleum mahogany sulfonates in organic solvents is normally not subject to reduction by the addition of relatively low viscous diluents or thinning Application November 23, 1946, Serial No. 711,837

10 Claims. (Cl. 252-334) agents. This requires agents of such relatively low viscosity that they interfere with the lubrieating properties 01' the composition. Furthermore, these solvents are then of the type which easily evaporate. This is particularly critical in the case of textile treating materials since the use of such thinning solvents will leave behind on the fibre upon evaporation a viscous sticky impregnant without adequate lubricating capacity on the fibre and will also interfere with the scourability of the impregnated material. On the other hand thinning with a solvent of the lubricant type diluent will not obtain the desired result as it is necessary to add so much of the diluent as to bring the sulfonate content to below that necessary for adequate emulsification or other purpose for which the composition is designed.

' Ones object of the invention comprises inter alia the viscosity reduction of petroleum mahogany sulfonates in organic solvent solutions.

Another object of the invention comprises viscosity reduced petroleum mahogany sulfonate solutions.

These and further objects of the invention will appear from the following description.

A suitable petroleum mahogany sulfonate solution in an organic substantially water immiscible solvent for said sulfonate is treated with at least one phthalic acid derivative selected .from the group consisting of substantially oil soluble phthalic acid esters of alkalene glycols, phthalic acid esters of alkylene glycol ethers and alkyl phthalates in amount suflicient to thereby appreciably lower the viscosity of said solution due to the sulfonate dissolved therein and preferably reduce said viscosity by at least one-third.

The solvents that may be used for this purpose should not appreciably dissolve inor anic salts and should be substantially liquid at normal temperatures. -Suitable solvents that may be used in the practice of the invention are, for

instance, petroleum oil distillates or any fraction In such cases it is of advantage that the boiling pain he so low and preferably between 75 and 250 as to enable the removal of the solvent at ordinary temperatures without the necessity of resorting to vacuum distillation.

The petroleum mahogany sulfonate which is subjected to the viscosity reduction is normally one derived from the acid refining, with fuming sulfuric acid, of a petroleum oil distillate stock under sulfonating conditions of acid amount and temperature in accordance with. conventional refining practice. In such conventional fuming sulfuric acid refining an oil layer and acid sludge layer are formed, the former containing dissolved therein petroleum mahogany sulfonic acids coilectively referred to as mahogany petroleum sulfonic acids. These are recovered from the oil layer in accordance with conventional methods in the form of solutions of these sulfonic acids or their salts (the latter being collectively termed petroleum mahogany sulfonates") in a portion of the oil relatively tenaciously occluded by these sulfonic bodies. This occluded oil is generally referred to in the art as retained" oil. The petroleum sulfonic acids or sulfonate oil compositions normally contain about 30 to 35% of retained oil and 65 to 70% of the petroleum mahogany sulfonic material. Depending upon the type and origin of petroleum oil distillates from which these sulfonate-oil solutions or stocks are derived they contain sulfonates of varying averaged molecular weights. For convenience therefore the sulfonate stocks are identified by their average molecular weights. Thus, a 420 or 450 sulfonate stock is a stock in which the sulfonates have an average molecular weight of 420 or 450 respectively.

The aforementioned group member materials should preferably be oil soluble, and good results are, for instance, obtained with diethylene glycol phthalate, phthalic acid ester of a diethylene glycol alkyl ether and preferably of diethylene glycol monethyl ether, phthalic acid ester of diethylene glycol monoethyl ether and of diethyiene glycol butyl ether and preferably of diethylene glycol monobutyl ether, an allryl phthalate including methyl, ethyl. butyl and amyl 'phthlate and preferably a dialkyl phthalate including diethyl, di-butyl, diamyl and preferably dimethyl .phthalate. The majority of the group member agents useful in accordance with the invention are oil soluble and substantially water insoluble. Within the scope of my invention and for best results I may use from 0.5 to and preferably from 1 to 3% of the viscosity reducing agent in accordance with the invention calculated by weight of sulfonates present in solution.

In the practical application of the invention, a suitable petroleum mahogany sulfonate solution in a solvent of the aforedescribed character and nature is intimately contacted with one or more of the aforementioned viscosity reducing agents. The mix is preferably agitated and the treatment continued until the desired viscosity reduction is obtained which is usually achieved quite rapidly. In fact, in many cases the desired viscosity reduction is obtained once thorough intermingling of the components is procured.

The temperature of reaction is ordinarily .not critical. The reaction, howevenmay be facilitated by increasing the temperature to for example a preferred temperature of from 120 to 200 F. This is particularly desirable with more heavily viscous solutions as the higher temperature will lntitefii? the fluidity of the solution, thus ermitting more intimate contact between the reactants.

s The extent to which low viscosity values may be obtained depends, at least to some extent. upon the type or origin of the. petroleum mahogany sulfonate selected for the treatment. Ordinarily higher average molecular weight sulfonates possess a higher viscosity and the resulting viscosity after treatment is usually commensurately higher than the viscosity after treatment of a comparative sulfonate hydrocarbon solution which before treatment possessed a relatively lower viscosity and in which the sulfonate had a lesser average molecular weight.

The ratio of petroleum mahogany sulfonate to a solvent is, as a rule, not critical except that it is" desirable to so adjust the ratio that the viscosity of the solution is sumciently low at the desired or selected temperature of treatment to permit the intimate contact between the reactants. In most cases, however, a ratio of mahogany sulfonate to solvent of substantially 2 to l (by weight) will give satisfactory results. Sulfonate concentrations above 70 to 75% sulfonate content are normally not desirable for direct reaction without suitable extension. As a mode of agitation, any conventional method 'such as stirring, air'-blowing, shaking, etc., may be used.

As above pointed out, the viscosity reducing treatment in accordance with the invention may be carried out with an organic solvent solution containing relatively high concentrations of petroleum mahogany sulfonate. In this case the resultant product is a concentrate which in many cases must be thereafter adjusted by the addition of organic solvent material of suitable viscosity, such as a suitable lubricant hydrocarbon, to the requisite petroleum mahogany sulfonate content desired for the specific purposefor which the composition'is to be used. Thus, for instance, if it is desired to ultimately produce a textile treating oil having in excess of 28% petroleum mahogany sulfonate and a viscosity of less than 600 seconds Saybolt at 100 F., a concentrate having in excess of 40% and usually between 60 and 65% sulfonate, is first obtained after the viscosity reducing treatment in accordance with the invention, which product may be then extended by the addition of a suitable lubricant hydrocarbon such as a mineral pale oil having a viscosity of seconds Sayboit at F. to a sulfonatecontent between 28 and 40% and a viscosity below 600 seconds Say bolt at 100 F.

Alternatively, the viscosity reducing treatment may be carried out with an organic solvent solution of a petroleum mahogany sulfonate already possessing the requisite final sulfonate content desired and intended for the purpose for which the viscosity reduced product is to be used. In that case it is also of advantage to select for the solution such solvent as is desired for the final product, i. e.,-if a textile lubricating oil is intended to be ultimately obtained a textile lubricant, having, for instance, a viscosity between '40 and seconds saybolt at 100 F. is selected as the solvent for the sulfonate. The product resultingfrom the viscosity reducing treatment is then per se usable after such further refining or purification as may be required for a textile treating 011.

Though in the operation of the novel viscosity reducing process any of the aforementioned solvents maybe used with advantage, I prefer to use as the solvent that hydrocarbon fraction, the Mid refining Of which furnished the crude mal hogany sulfonate stock and which is carried retained" oil. The crude mahogany sulfonate!" Example I 100 lbs. of a petroleum mahogany sulfonate stock (sodium sulfonates) containing about 62% sulfonate and about 8% "retained oil was used. The stock was obtained from a Mid-Continent distillate subjected to conventional white oil refining with fuming sulfuric acid under sulfonating conditions. The mahogany sulfonates in the stock possessed an averagemolecular weight of 450. The stock possessed a Furol viscosity of 141 at 210 F. and upon extension with a mineral pale oil (75 seconds Saybolt at 100 F.) to a 30% sulfonate content a viscosity of 2.145 seconds Saybolt at 100 F.

About 3 lbs. oi dimethyi phthalate were intimately mixed with the non-extended sulfonate stock at a temperature for the stock of about 180 F. The stock was agitated while the phthalate was being added and agitation was continued until a sample exhibited a Fural viscosity of 28 seconds at 210 F. Upon extension to a 30% sulfonate content with the aforementioned 75 vis. mineral pale oil a'viscosity of 384 seconds Saybolt at 100 F. was noted.

Example II I 100 lbs. of the same 450 (141 Furol at 210 F.) stock used in Example I was admixed with about 3 lbs. 01' diethylene glycol monobutyl ether phthalate following the procedure outlined in Example I. The agitation was continued until a sample exhibited a Furol viscosity of 32 sec- ,onds at 210 F. Upon extension to a 30% sulfonate content with the 75 vis. mineral pale oil specified in Example I a viscosity of 412 seconds Saybolt at 100 F. was noted.

Example [I] at 100 F. was observed.

The foregoing description is for purposes of illustration and not of limitation and it is therefor my intention that the invention be limited only by the appended claims or their equivalents wherein I have endeavored to claim broadly all inherent novelty.

I claim:

1. A viscosity reduced petroleum mahogany sulfonate solution which essentially consists of a petroleum mahogany sodium sulfonate solutionin an organic substantially water immiscible solvent for said sulfonate having normally a relatively high viscosity due to saidsulfonate dissolved therein of in excess of 600 seconds Saybolt at 100 F. for a sulfonate content of at least 28%,

- and. substantially dissolved in said solution at least one phthalic acid derivative selected from the group consisting of substantially oil soluble phthalic acid esters of alkylene glycols, phthalic acid esters of alkylene phthalates in amount sufficient to appreciably reduce said normally high viscosity to below 600 seconds Saybolt at F.

2. A viscosity reduced petroleum mahogany sulfonate solution in accordance with claim 1 in which said group member is present in amount sufilcientto reduces said normally high viscosity tively high viscosity due to said sulfonate dissolved therein of in excess of 600 seconds Saybolt at 100 F. for a sulfonate content of at least 28%, and, substantially dissolved in said solution, a substantially oil soluble phthalic acid ester of an alkyl ether of an alkylene glycol in amount sufilcient to reduce the said normally high viscosity by at least one-third to below 600 seconds Saybolt at 100 F.

5. A viscosity reduced petroleum mahogany sufonate solution in accordance with claim 4 in which said phthalic acid ester of an alkyl ether of an alkylene gycol is the phthalic acid ester of monoethyl ether of diethylene glycol.

6. A viscosity reduced petroleum mahogany sulfonate solution in accordance with claim 4 in which said phthalic acid ester of an alkyl ether of an alkylene glycol is the phthalic acid ester of monobutyl ether of diethylene glycol.

7. Aviscosity reduced petroleum mahogany sufonate solution which essentially consists of a petroleum mahogany sodium sulfonate solution in an organic substantially water. immiscible solvent for said sulfonate having normally a relatively high viscosity due to said sulfonate dissolved therein of in excess of 600 seconds Saybolt at 100 F. for a sulfonate content of at least 28%, and, substantially dissolved in said solution, a substantially oil soluble dialkyl phthalate in amount sufllcient to reduce said normally high viscosity by at least one-third to below 600 seconds Saybolt at 100.F.

8. A viscosity reduced petroleum mahogany sulfonate solution in accordance with claim 7 in which said dialkyl phthalate is dimethyl phthalate.

9. A viscosity reduced petroleum mahogany sulfonate solution which essentially consists of a solution of in excess of 28% petroleum mahogany sodium sulfonate in a solvent for said sulfonate of the petroleum hydrocarbon type having a viscosity substantially between 40 and seconds Saybolt at 100 F., said .solution having normally a viscosity appreciably in excess of 600 seconds Saybolt at 100 F. due to said sulfonate dissolved therein, and, substantially dissolved in said solution, at least one phthalic acid derivative selected from the group consisting of substantially oil soluble phthallc acid esters of alkylene glycols. phthalicacid esters of alkylene glycol ethers and alkyl phthalates in amount sufllclent to reduce said viscosity appreciably in excess of 600 seconds Saybolt at 100 F. to a pointsufilciently low to yield for a sulfonate content in excess of 28%. a iscosity below 600 seconds Saybolt at 100 F.

10. A substantially self-scouring lubricated textile material which comprises a textile mateglycol ethers and alkyl- 7 rial impregnated with a viscosity reduced petroleum mahogany sulfonate solution essentially consisting of a petroleum mahogany sodium suli'onate solution in an organic substantially water immiscible solvent for said sulionate having normally a relatively high viscosity due to said sulfonate dissolved therein of in excess of 600- REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,408,971 Duncan Oct. 8, 1945 2,401,614 Chechot -1 June 4, 1946 2,338,522 Liberthson Jan. 4, 19% 2,215,590 Maverick Sept. 24, 1940 2,212,369 Jaeger Aug. 20, 1940 Certificate of Correction Patent No. 2,454,825. November 30, 1948.

JACOB FAUST It is, hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 5, line 13, for 8% read 38%; column 6, line 8, claim 2, for reduces read reduce;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 29th day of March, A. D. 1949.

THOMAS F. MURPHY,

Assistant Gammissioner of Patents. 

